The dinuclear PhotoCORM (CO)<sub>3</sub>(bpy)ReMn(CO)<sub>5</sub>. formation of a luminactive product upon CO uncaging by MMLCT excitation
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We report a photochemical investigation of the dinuclear metal carbonyl complex (CO)<sub>3</sub>(bpy)ReMn(CO)<sub>5</sub>, where bpy = 2,2′-bipyridine. This investigation follows an earlier study of the photo-activated carbon monoxide release as the result of long-wavelength visible and near-infrared excitation of a several different (CO)<sub>5</sub>ReMn(CO)<sub>3</sub>(LL) complexes in aerobic media. These dinuclear species all show a strong metal − metal-bond (σ<sub>MM</sub>)-to-ligand (π<sub>L</sub>*) charge-transfer (MMLCT) bands as the lowest energy absorptions in their respective optical spectra. Photolysis of the MMLCT band leads to homolysis of the metal-metal bond to give mononuclear metal radicals that can be trapped with dioxygen. The species formed from the manganese carbonyl radical fragments undergo CO release <i>via</i> secondary reactions, while the mononuclear product(s) formed from the •Re(CO)<sub>3</sub>(bpy) radical is luminescent. In these contexts, we discuss potential applications of such dinuclear compounds as photoactivated CO-releasing moieties.
